PVDF-HFP-SN-based gel polymer electrolyte for high-performance lithium-ion batteries

Gel polymer electrolytes(GPEs)have attracted extensive attention in lithium-ion batteries due to their high security and excellent electrochemical performance.However,their inferior Li-ion transference number,low room-temperature ionic conductivity,and poor long cycle stability raise challenges in practical applications.Herein,a flexible poly(vinylidene fluoride-cohexafluoropropylene)-butanedinitrile(PVDF-HFP-SN)-based GPE(PSGPE)is synthesized successfully by a general immersion precipitation method.The resultant PSGPEs have numerous connecting pores to ensure sufficient space for liquid electrolytes.Moreover,the reduced crystallinity of PVDF-HFP and the high polarity of SN can reduce the energy barrier of Li-ions shuttling between pores.The synergistic effect possesses a high ionic conductivity of 1.35 mS·cm^(-1)at room temperature with a high Li-ion transference number of 0.69.The PVDF-HFP-SN-based GPE is applied in a LiFePO_(4)/graphite battery,which can realize stable cycling performance for 350 cycles and good rate performance at room temperature.These results demonstrate that the novel PSGPE possesses advantage in simplified production process,which can improve the practicability of gel polymer lithium-ion batteries.

A functional gel polymer electrolyte based on PVDF-HFP/gelatin toward dendrite-free lithium metal batteries

The leakage of liquid electrolyte and the formation of lithium dendrites pose challenges to safety and stability of lithium metal batteries(LMBs).The appearance of gel polymer electrolyte(GPE)has obviously improved the safety of traditional LMBs.However,the limited inhibition of GPE on lithium dendrites is detrimental to the safety of LMBs.Herein,a kind of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)/gelatin(GN)GPE with high ionic conductivity,high-temperature resistance,and flame-retardancy,was prepared by electrospinning and soaking method.Utilizing the electrospinning network of PVDF-HFP,its affinity to liquid electrolytes,makes this GPE more beneficial to ions transport and the formation of gel.And,the GN with sol–gel properties,enhances the mechanical property(13.5 MPa)of HFP-GN GPE.Meanwhile,X-ray photoelectron spectroscopy(XPS)and density functional theory(DFT)suggest that the attraction of polar groups of GN to Li+can regulate the distribution of Li+and protect Li anodes.Consequently,the application of HFP-GN GPEs to LMBs with cathodes of LiFePO_(4) and LiCoO_(2) deliver excellent electrochemical performances:after 300 cycles,the LiFePO_(4)/HFP-GN GPE/Li battery keeps a low capacity decay rate of 0.09%at 5 C;after 400 cycles at 2 C,the LiCoO_(2)/HFP-GN GPE/Li cell retains a high capacity retention of 74%.This GPE is demonstrated for the application prospect of safe LMBs.

Anion-immobilized solid composite electrolytes based on metal-organic frameworks and superacid ZrO_(2) fillers for high-performance all solid-state lithium metal batteries

Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.

刚柔并济的仿生凝胶聚合物电解质助力稳定的锂电池

凝胶聚合物电解质(GPE)因其优良的热稳定性和卓越的电化学性能而具备增强锂离子电池性能的潜力,从而受到越来越多的认可.尽管其具有上述优点,但传统GPE的实际应用通常因其溶胀性和有限的机械强度而受到阻碍.为了解决这些问题,本项研究工作提出了一种通过简单方法构建的刚柔并济的仿生GPE,由聚环氧乙烷(PEO)和聚偏二氟乙烯-六氟丙烯(PVDF-HFP)组成并通过Kevlar纤维织物进行增强.所得的PEO/PVDF-HFP/Kevlar(PPK)GPE表现出2.815 mS cm^(−1)的优异离子电导率和0.571的锂离子迁移数,以及32.59 MPa的超高机械强度.这些特性有助于防止锂枝晶生长并增强LiFePO4电池的电化学性能,从而实现稳定的循环性能.PPK GPE可以为高性能锂离子电池的各种实际应用提供理论基础.

=unctional interlayer of PVDF-HFP and carbon nanofiber for long-life lithium-sulfur batteries

In the present work we develop a scalable and inexpensive design for lithium- sulfur （Li-S） batteries by capping a flexible gel polymer/carbon nanofiber （CNF） composite membrane onto a free-standing and binder-free CNF ＋ ni2s6 cathode, thus achieving a three-dimensional （3D） structural design. The CNF network is used as the current collector and S holder to overcome the insulating nature and volume expansion of S, while the composite membrane comprises a gel polymer poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP）, and CNF additive is used as an interlayer to trap polysulfides and recycle the remaining S species, leading to a high specific capacity and long cycle life. This 3D structure enables excellent cyclability for 500 cycles at 0.5℃ with a small capacity decay of 0.092% per cycle. Furthermore, an outstanding cycle stability was also achieved at even higher current densities （1.0 to 2.0℃）, indicating its good potential for practical applications of Li-S batteries.